Sunscreen safety and efficacy enhancement

ABSTRACT

The present invention discloses safety and efficacy enhancement of sunscreens with certain heterocyclic base complexes of manganese via urocanate pathway modulation. The present invention also discloses a method for topical application of said complexes, which causes the reduction of topical peroxide including hydrogen peroxide, the reduction of topical inflammation including sunburn, increased sun protection of skin, the reduction of skin wrinkles, comprehensive protection from UVA, UVB, and UVC, and reduction of radiation-initiated inflammation.

The present invention is a continuation-in-part of U.S. patentapplication Ser. No. 11/308,290; filed Mar. 15, 2006, which is acontinuation-in-part of U.S. patent application Ser. No. 10/306,948filed Nov. 29, 2002, now abandoned. The present invention is also acontinuation-in-part of U.S. patent application Ser. No. 10/710,011,filed Jun. 11, 2004 now abandoned.

BACKGROUND OF THE INVENTION

The present invention discloses safety and efficacy enhancement ofsunscreens with certain heterocyclic base complexes of manganese viaurocanate pathway modulation. The present invention also discloses amethod for topical application of said complexes, which causes thereduction of topical peroxide including hydrogen peroxide, the reductionof topical inflammation including sunburn, increased sun protection ofskin, the reduction of skin wrinkles, comprehensive protection from UVA,UVB, and UVC, and reduction of radiation-initiated inflammation.

DETAILED DESCRIPTION

The present invention discloses safety and efficacy enhancement ofsunscreens with certain heterocyclic base complexes of manganese viaurocanate pathway modulation. The topical application of compositions ofthe present invention causes the reduction of topical peroxide includinghydrogen peroxide, the reduction of topical inflammation includingsunburn, increased sun protection of skin, the reduction of skinwrinkles, comprehensive protection from UVA, UVB, and UVC, and reductionof radiation-initiated inflammation.

The present invention also relates to a method for topical applicationof certain heterocyclic complexes of manganese as catalase mimetics forthe reduction of topical hydrogen peroxide, the latter known to beformed by the action of UV on certain sunscreen agents in the presenceof moisture. This results in the enhancement of both the safety andefficacy of said sunscreen agents. The method of topical delivery of thepresent invention comprises; (i) mixing of a manganese complex of anitrogen heterocyclic base, wherein manganese is covalently bound to atleast two oxygen atoms and, wherein, said base having at least onenitrogen atom in its ring structure coordinately bound to saidmanganese, and having general chemical structure according to [FIG. 1];and (ii) a sunscreen agent; and (iii) topical application of saidmixture. Alternatively, said manganese complex can be generated on-siteon skin surface by the reaction of a manganese donor agent with asuitable nitrogen heterocyclic base already present on skin surface. Acosmetically or pharmaceutically acceptable carrier base can also beincluded with the said mixture.

The said method causes the reduction of peroxides, such as hydrogenperoxide, formed from the exposure of a sunscreen agent to UV or solarradiation in the presence of topical moisture on skin. The said methodis useful for enhancing the safety and efficacy of topical sunscreenagents. The anti-inflammatory, wrinkles reduction, skin aging control,cellular antioxidant, and skin damage control benefits that are a resultof the reduction of said peroxides on skin are also provided by themethod of the present invention.

Sunscreen compositions, which protect skin from the damaging effects ofsolar UV, are now widely used by consumer for their various protectivebenefits, for example, skin cancer, collagen breakdown, abnormal elastinaccumulation, free radicals accumulation that damages cell function andalters genetic material, and certain chemicals that are released thatsuppresses the immune system.

Sunscreens offer full protection against UVB, but not UVA. Very fewsunscreen ingredients protect against UVA. Three types of UV is givenoff by the sun; (1) UVC (100-290 nm): it is absorbed by the ozone anddoesn't affect the skin, as it usually does not reach the Earth; (2) UVB(290-320 nm): it affects the outer layer of the skin and is the primarycause of sunburn. It is most intense between 10-2 and during the summermonths; and (3) UVA (320-400 nm): it penetrates deeper into the skin andthe intensity is more constant than UVB without variations through theday and year. These aspects have been further discussed in detailelsewhere, for example, Reisch et al. [Chemical & Engineering News, 83,18 (2005].

It is now becoming clear that certain sunscreens cause the formation ofhydrogen peroxide upon their exposure to UV in the presence of moisture.It is actually this peroxide that causes the breakdown of collagen,damages to cell function, and suppression of the immune system.

It is also becoming clear that urocanic acid, formed from the action ofHistidine Ammonia Lyase on L-Histidine, which acts as a naturalsunscreen agent on skin, for example Stab et al., U.S. Pat. No.5,620,680, is converted into its cis-isomer upon exposure to UV, thelatter then catalyzes the formation of various peroxide species via acascade of urocanate pathway biochemical steps [FIG. 2]:

The role of manganese in enhancing the efficacy of sun-block agents hasbeen recognized very recently. For example, manganese ions introduceextra energy levels in titanium dioxide, a very popular sun-block agent.These energy levels sit in the UVA portion of the absorption band. Thisallows for the higher absorption levels for titanium dioxide. Manganesealso causes the free radical scavenging on skin [FIG. 3]:

Manganese doping of sun-block agents has thus become a recent practice.Wakefield et al. [Photochem. Photobiol. Sci., 3, 648 (2004)] report theeffect of manganese doping on the free radical generation rate, freeradical scavenging, and UVA absorption properties of titania. Theseauthors do not disclose any peroxide reducing benefits of said doping.Wakefield et al. do not disclose any methods for the said doping of anyorganic sunscreen agents.

In a product description, Oxonica (www.oxonica.com) similarly disclosesmanganese doping of titanium dioxide for free radical scavengingbenefits. Any methods for the said doping of any organic sunscreenagents and its effect on peroxide degradation were not disclosed.

Sakurai et al. [Photochem. Photobiol Sci., 4, 715 (2005] disclose theharmful effects of ultraviolet (UV) exposure on the skin that areassociated with the generation of reactive oxygen species (ROS) such assuperoxide anion radical [O(2)(−)], hydrogen peroxide [H(2)O(2)],hydroxyl radical (OH), and singlet oxygen [(1)O(2)] as well as lipidperoxides and their radicals (LOOH and LOO). Again, the problem wasidentified, but no solutions were proposed.

Hayashi et al. [Toxicol. Lett., 167, 1 (2006)] disclose benzophenone(BP) to be a suspected endocrine disrupter that is found in theenvironment. BP undergoes metabolic and photochemical activation.Hayashi et al. identified photoproducts of BP using high-performanceliquid chromatography and mass spectrometry, and determined theirestrogenic activity using both in vitro and in vivo assays. Although BPshowed no estrogenic activity, two estrogenic photoproducts weredetected after irradiating an aqueous solution of BP with UV orsunlight. These active products were identified as 3-hydroxy BP (BP-30H)and 4-hydroxyBP (BP-40H). The formation of hydrogen peroxide H2O2) wasdetected with increasing levels of UV, and the addition of H2O2 to theBP solution increased BP-30H and BP-40H production under UV irradiation.BP hydroxylation was also observed in the reaction with the Fentonreagent generating hydroxyl radical without UV irradiation. Theseresults suggest the involvement of photochemically generated H2O2 andhydroxyl radical in the BP hydroxylation. BP-40H was more potent thanBP-30H for promoting estrogen receptor (ER)-mediated transcription anduterotrophic activity, although both of them showed same affinity in ERbinding. In conclusion, BP can be converted into ring-hydroxylatedderivatives that have estrogenic activity after exposure to light. WhileHayashi et al. did show harmful effects of a commonly used sunscreenagent, such as benzophenine-3, including peroxide formation, they didnot disclose any solution to this problem.

Yashui et al., [Biochem. Biophys. Res. Commun., 269, 131 (2000)] reportthat the recent increase of ultraviolet (UV) rays on Earth due to theincreasing size of the ozone hole is suggested to be harmful to life andto accelerate premature photoaging of the skin. The detrimental effectsof UV radiation on the skin are associated with the generation ofreactive oxygen species (ROS) such as superoxide anion radical, hydrogenperoxide (H(2)O(2)), hydroxyl radical (HO.), and singlet oxygen[(1)O(2)]. However, direct proof of such ROS produced in the skin underUV irradiation has been elusive. In this study, Yashui et al. reportfirst in vivo detection and imaging of the generated ROS in the skin oflive mice following UVA irradiation, in which both a sensitive andspecific chemiluminescence probe (CLA) and an ultra low-light-imagingapparatus with a CCD camera were used. In addition, these authors foundthat superoxide radical anion is formed spontaneously and (1)O(2) isgenerated in the UVA-irradiated skin.

Nishimura et al: [Exp. Dermatol., 15, 891 (2006)] have shown theformation of reactive oxygen species (ROS) in the skin induced by theultraviolet (UV) light that has been shown to lead to many cutaneousdisorders, skin cancer and photo ageing, the mechanism and distributionof ROS generation has not yet been definitively determined. Nishimura etal. have thus shown that ROS induced by UVA exposure occurs anddistributes in the outermost layer of the stratum corneum.

Radschuweit et al. [Photochem. Photobiol., 73, 119 (2001] report topicalapplication of Ketoprofen (KP), which is a potent nonsteroidalanti-inflammatory drug, to be problematic because the photosensitizingproperties of the benzophenone moiety that may cause phototoxic effectswhen the treated skin region is exposed to UVA light. Using capillaryelectrophoresis with electrochemical detection a high amount of hydrogenperoxide was found among the reaction products. This shows potential forharmful effects on topical application of other benzophenonederivatives, such as certain organic sunscreen agents.

Patt (U.S. patent application Ser. No. 20060246029) discloses certainpeptide manganese complexes, which also contain retinal, for thetreatment of photo-damaged skin. Patt does not disclose any peroxidereducing benefits of said manganese complexes.

Patt (U.S. patent application Ser. No. 20060018851) also discloses thetreatment for hyperpigmentation with certain peptide manganesecomplexes, which also contain retinal. Patt does not disclose anyperoxide reducing benefits of said manganese complexes.

Manganese complexes have been known for some time, for example, Gupta(U.S. patent application Ser. No. 20060183708), which does not discloseany peroxide reducing benefits of said complexes on their topicalapplication. San et al. [Z. Naturforsch., 59, 692 (2004)] disclosecertain metal complexes of amino acid Schiff's bases.

Sayre et al. [Photochem. Photobiol., 81, 452 (2005] report the formationof free-radicals upon exposure of organic sunscreens to UV. While it didshow the problem, Sayre et al. did not produce a solution.

From the above discussion it is clear that hydrogen peroxide and otherperoxy species are formed on skin surface by the action of UV. Theformation of such peroxides increases in the presence of certainsunscreen and sun-block agents. The harmful effects of such accumulationof peroxide species on skin are also well recognized by the medical andscientific community. It is thus surprising that no effective solutionto this problem has been disclosed until the present invention.

In an unexpected and surprising discovery, the present inventiondiscloses certain manganese complexes of nitrogen heterocyclic bases,wherein manganese is covalently bound to at least two oxygen atoms andcoordinately bound to at least one nitrogen atom, and having generalchemical features shown in [FIG. 1], that cause a reduction of peroxidespecies on skin. This benefit is provided even when said manganesecomplexes of nitrogen heterocyclic bases are used in combination with asunscreen or sun-block agent(s). A method for the topical application ofsaid manganese complexes of nitrogen heterocyclic bases to provide saidreduction of peroxide species on skin is also disclosed. A covalent bondis formed by the sharing of electrons between two atoms. A coordinatebond, or dative bond, is formed when an electron-donor species (aLewis-base) donates a pair of electrons to an electron acceptor species(a Lewis-acid).

Urocanic acid, as discussed above, catalyzes the formation of peroxidesfrom the action of UV on skin. In a yet another surprising discovery,certain manganese derivatives of urocanic acid, have now been found tocatalyze the decomposition of said peroxides on skin. It is postulatedthat said manganese derivative of urocanic acid first undergoes aphotoisomerization, and the photoisomerized form subsequently causes thedecomposition of peroxides [FIG. 4]:

The manganese complexes of the present invention can also be in an openconfiguration, such as manganese complexes of certain nucleotide bases,as exemplified in [FIG. 5].

The examples of said manganese complexes include manganese urocanate,manganese urocanate glycinate, manganese urocanate gluconate, manganeseadenosine triphosphate, manganese adenosine diphosphate, manganeseadenosine mono-phosphate, manganese adenosine triphosphate glycinate,manganese adenosine triphosphate amino acetate, manganese adenosinediphosphate amino acetate, manganese adenosine mono-phosphate aminoacetate, manganese benfotiamine glycinate, manganese benfotiamine,manganese benfotiamine amino acetate, manganese benfotiamine gluconate,and combinations thereof.

It is well known that catalases are responsible for the decomposition ofperoxides, such as hydrogen peroxide, to water and oxygen. Catalasescontain four porphyrin heme (iron) groups. There are no topically knowncatalases, however. The accumulation of hydrogen peroxide on skin isthus dangerous for human health. The catalase-type decomposition oftopical hydrogen peroxide by manganese complexes of the presentinvention is thus both unexpected and surprising. Although the mechanismof this action is not fully known yet, it is postulated that bothmanganese and a heterocyclic nitrogen atoms are responsible for afive-center transition state for the decomposition of two moles ofhydrogen peroxide to two moles of water and an oxygen molecule via acatalytic mechanism shown in [FIG. 6].

Since it is well known that urocanic acid is present on skin surface insufficient quantities, the present invention also discloses a novel andsimple method for the formation of manganese urocanate complexes viain-situ conversion of said urocanic acid by its contact with manganesecomplexes of certain nucleotide bases, such as those exemplified in[FIG. 6], which includes manganese adenosine triphosphate, manganeseadenosine diphosphate, manganese adenosine mono-phosphate, manganeseadenosine triphosphate glycinate, manganese adenosine triphosphate aminoacetate, manganese adenosine diphosphate amino acetate, manganeseadenosine mono-phosphate amino acetate, manganese benfotiamineglycinate, manganese benfotiamine, manganese benfotiamine amino acetate,manganese benfotiamine gluconate, EUK-134[((N,N′-bis(3-methoxysalicylidene)ethylenediamine)) Manganesechloride)], and combinations thereof.

In a yet another surprising discovery, the manganese urocanate complexesof the present invention also cause a skin soothing effect via theirreduction of topical hydrogen peroxide. The exact mechanism of thisbenefit is still unknown. It is possible that the reduction of peroxidescan also reduce the formation of other peroxides on skin that may beinflammatory. This anti-inflammatory effect of the manganese urocanatecomplexes of the present invention is unprecedented. This soothingeffect is also useful for both prevention and treatment of sunburn. Thepresent disclosure is both unexpected and surprising in view ofKammeijer et al. (U.S. Pat. No. 7,056,938) who have disclosed thaturocanic acid actually causes irritation due to its immunosuppressioneffect on skin.

The amount of manganese complexes of present invention in a compositioncan be from catalytic amounts, for example 0.0001 percent, to anydesired higher amount. These manganese complexes can be immobilized on apolymer matrix, such as polypore, or on porous surfaces, such aszeolites, silicates, or aluminates.

Urocanates and their various applications have been known for a while.

Gers-Barlag et al. (U.S. Pat. No. 5,658,556) have disclosedhydrophobicized, pharmaceutically or cosmetically acceptable inorganicpigments in cosmetic or dermatological preparations for preventingleaching out or washing off of the skin's cis- or trans-urocaninic acidfrom the human skin, caused by the action of water, or leaching out orwashing off of cis- or trans-urocaninic acid which has been appliedartificially to the skin, from the human skin caused by the action ofwater.

Kim et al. (KR890000113B) disclose a method for preparing uv absorbentpowder comprises (i) dispersing inorganic or organic powder, forexample, TiO2, kaolin, silk powder, mica, acryl powder into water, (ii)dissolving multivalent metal salt such as Al2(SO4)3 18H2O to adsorb Al(III) ion onto powder surface, (iii) adding uv absorbent such as Na saltof N,N-dimethyl-p-amino-benzoic acid,N,N-dihydroxypropyl-p-amino-benzoic acid or urocanic acid and (iv)washing with water, centrifugally separating and drying.

Kammeijer et al. (EP 1196219) disclose UV absorbing benefits oftrans-urocanic acid.

Gers-Barlag et al. (U.S. Pat. No. 6,372,199) disclose use of one or moreunsymmetrically substituted s-triazine derivatives in cosmetic ordermatological preparations for preventing the washing out or washingoff, caused by the action of water, of endogenous skin cis- andtrans-urocanic acid from human skin or the washing out or washing off,caused by the action of water, of cis- and trans-urocanic acid appliedartificially to the skin from human skin.

Takanabe et al. (JP 8059446) disclose a two-phase type UV raysprotective cosmetic containing an oily UV absorbent, oil-absorbingpowder and an aqueous medium. The oily UV absorbent contains anaminobenzoate-based, salicylate-based, cinnamate-based,benzophenone-based or urocanic acid-based ultraviolet absorbent orvitamins. The oil absorbing powder contains an oil absorbing powder. Theoil-absorbing powder is composed of a natural organic polymer, asynthetic organic polymer or a natural organic polymer or a complex ofthe synthetic organic polymer with an inorganic compound. Takanabe etal. do not disclose any peroxide decomposing or SPF enhancing benefitsof their compositions. The use of urocanic acid in Takanabe disclosureappears to be for its UV absorbing benefits only.

Sauermann et al. (WO 9420065) disclose the use of an effective quantityof trans-urocanic acid as an antioxidant, optionally in a suitablegalenical carrier, for cosmetic and/or dermatological purposes, as wellas the use of an effective concentration of trans-urocanic acid as anantioxidant in cosmetic and dermatological formulations.

Diesel et al. (DE 4122497) disclose a composition for externalapplication and treatment (in conjunction with UV irradiation) ofinflammatory skin diseases comprises (1) incorporating trans-urocaninicacid (1) into a carrier material, then (2), either on the body surfaceor in vitro, irradiating the composition with UV light. (I) is thusconverted to cis-urocaninic acid (II) which has immunosuppressantactivity on cytotoxic lymphocytes. The process is used to treat orprevent psoriasis. Diesel et al. do not disclose any peroxide reducingbenefits of their compositions.

Furantsu et al. (JP 4230321) disclose a dermatological composition fortreatment and prophylaxis of inflammatory dermatoses and care andrestoration of sensitive and stressed skin, which comprises an effectiveamount of cis-urocanic acid and/or its derivative.

Yamamoto et al. (JP 1117868) disclose urocanic acid derivatives usefulas UV absorbers.

The preparation of manganese complexes of nitrogen heterocyclic bases ofthe present invention can be very simple. In most cases, the mixing ofan ammonium, alkali metal, or alkaline earth metal salt of a nitrogenheterocyclic carboxylic acid or phosphoric acid with a manganese donoragent, which can be an organic or an inorganic donor agent, results inthe formation of said manganese complexes. Various in-situ processes canalso achieve the preparation of said manganese complexes. Certain othercomplexes, such as EUK-134, may require a more sophisticatedmanufacturing process.

The sunscreen component of the compositions of the present invention isselected from a large number of such sunscreen and sun-block agentsavailable today that includes zinc oxide, galanga extract, titaniumdioxide, PABA, Avobenzone, 3-Benzylidene camphor, Benzylidene camphorsulfonic acid, Bisymydazilate, Camphor Benzalkonium Methosulfate,Polyquaternium-59, Cinnamidipropyltrimonium chloride, Diethylaminohydroxybenzoyl hexyl benzoate, Diethylhexyl butamido triazone,Dimethicodiethylbenzal malonate, Drometrizole trisiloxane, Ecamsule,Ensulizole, Homosalate, Isoamyl p-methoxycinnamate, 4-Methylbenzylidenecamphor, Octocrylene, Octyl Dimethyl PABA, Cinoxate, Dioxybenzone, Octylmethoxycinnamate, Octyl salicylate, Octyl triazone, Oxybenzone, PEG-25PABA, Polyacrylamidomethyl benzylidene camphor, Sulisobenzone, Methylanthranilate, Trolamine salicylate, Benzophenone-3, Benzophenone-4,Tinosorb M, Tinosorb S, and mixtures thereof.

Certain sunscreen compositions disclosed earlier by the present inventor(U.S. patent application Pre-grant publication No. 20050276761; whichcorresponds to U.S. patent application Ser. No. 10/710,011, filed Jun.11, 2004), when used in combination with manganese complexes of thepresent invention provide greatly improved skin protection from UV andperoxide including hydrogen peroxide. This is further illustrated inExamples 14 to 17.

For topical application to the skin, the compositions of the presentinvention may be provided in any cosmetic or pharmaceutical formnormally used in the cosmetics and dermatological fields, and it may inparticular be in the form of an aqueous, optionally gelled, solution, ofa dispersion of the optionally two-phase lotion type, of an emulsionobtained by dispersion of a fatty phase (oil) in an aqueous phase (O/W)or vice versa (W/O), of a triple emulsion (W/O/W or O/W/O) or of avesicular dispersion of the ionic and/or nonionic type. Thesecompositions may be prepared according to the usual methods. Thiscomposition may be more or less fluid and have the appearance of acream, an ointment, a milk, a lotion, a serum, a paste, a powder, and amousse. It may optionally be applied in the form of an aerosol. It mayalso be provided in solid form, in particular in the form of a stick. Itmay be used as a care product and/or as a make-up product for the skin.It may also be used as a shampoo or a conditioner.

The compositions of the present invention can be formulated in variouscosmetic and pharmaceutical consumer products utilizing a variety ofdelivery systems and carrier bases. Such consumer product forms includethe group consisting of shampoos, aftershaves, sunscreens, body and handlotions, skin creams, liquid soaps, bar soaps, bath oil bars, shavingcreams, conditioners, permanent waves, hair relaxers, hair bleaches,hair detangling lotion, styling gel, styling glazes, spray foams,styling creams, styling waxes, styling lotions, mousses, spray gels,pomades, shower gels, bubble baths, hair coloring preparations,conditioners, hair lighteners, coloring and non-coloring hair rinses,hair grooming aids, hair tonics, spritzes, styling waxes, band-aids, andbalms.

In another preferred aspect, the delivery system can be traditionalwater and oil emulsions, suspensions, colloids, micro emulsions, clearsolutions, suspensions of nanoparticles, emulsions of nanoparticles, oranhydrous compositions.

The compositions of the present invention may also contain adjuvantswhich are used in the cosmetics field, such as hydrophilic or lipophilicgelling agents, hydrophilic or lipophilic active agents, preservingagents, antioxidants, solvents, fragrances, fillers, screening agents,pigments, odor absorbers and dyestuffs. The amounts of these variousadjuvants may be those conventionally used in the field considered.These adjuvants, depending on their nature, can be introduced into thefatty phase, into the aqueous phase or into the lipid vesicles. Inaddition, moisturizers may complete the effect obtained using thesapogenins according to the invention and anti-inflammatory agents arealso useful.

Additional cosmetically or pharmaceutically beneficial ingredients canalso be included in the compositions of the present invention, which canbe selected from skin cleansers, cationic, anionic surfactants,non-ionic surfactants, amphoteric surfactants, and zwitterionicsurfactants, skin and hair conditioning agents, vitamins, hormones,minerals, plant extracts, anti-inflammatory agents, collagen and elastinsynthesis boosters, UVA/UVB sunscreens, concentrates of plant extracts,emollients, moisturizers, skin protectants, humectants, silicones, skinsoothing ingredients, antimicrobial agents, antifungal agents, treatmentof skin infections and lesions, blood microcirculation improvement, skinredness reduction benefits, additional moisture absorbents, analgesics,skin penetration enhancers, solubilizers, moisturizers, emollients,anesthetics, colorants, perfumes, preservatives, seeds, broken seed nutshells, silica, clays, beads, luffa particles, polyethylene balls, mica,pH adjusters, processing aids, and combinations thereof.

In another preferred aspect, the cosmetically acceptable compositionfurther comprises one or more excipient selected from the groupconsisting of water, saccharides, surface active agents, humectants,petrolatum, mineral oil, fatty alcohols, fatty ester emollients, waxesand silicone-containing waxes, silicone oil, silicone fluid, siliconesurfactants, volatile hydrocarbon oils, quaternary nitrogen compounds,amine functionalized silicones, conditioning polymers, rheologymodifiers, antioxidants, sunscreen active agents, di-long chain aminesfrom about C.sub.10 to C.sub.22, long chain fatty amines from aboutC.sub.10 to C.sub.22, fatty alcohols, ethoxylated fatty alcohols anddi-tail phospholipids.

Representative saccharides include nonionic or cationic saccharides suchas agarose, amylopectins, amyloses, arabinans, arabinogalactans,arabinoxylans, carageenans, gum arabic, carboxymethyl guar gum,carboxymethyl(hydroxypropyl) guar gum, hydroxyethyl guar gum,carboxymethyl cellulose, cationic guar gum, cellulose ethers includingmethyl cellulose, chondroitin, chitins, chitosan, chitosan pyrrolidonecarboxylate, chitosan glycolate chitosan lactate, cocodimoniumhydroxypropyl oxyethyl cellulose, colominic acid ([poly-Nacetyl-neuraminic acid]), corn starch, curdlan, dermatin sulfate,dextrans, furcellarans, dextrans, cross-linked dextrans, dextrin,emulsan, ethyl hydroxyethyl cellulose, flaxseed saccharide (acidic),galactoglucomannans, galactomannans, glucomannans, glycogens, guar gum,hydroxy ethyl starch, hydroxypropyl methyl cellulose, hydroxy ethylcellulose, hydroxy propyl cellulose, hydroxypropyl starch,hydroxypropylated guar gums, gellan gum, gellan, gum ghatti, gum karaya,gum tragancanth (tragacanthin), heparin, hyaluronic acid, inulin,keratin sulfate, konjac mannan, modified starches, laminarans,laurdimonium hydroxypropyl oxyethyl cellulose, okra gum, oxidizedstarch, pectic acids, pectin, polydextrose, polyquaternium-4,polyquaternium-10, polyquaternium-28, potato starch, protopectins,psyllium seed gum, pullulan, sodium hyaluronate, starchdiethylaminoethyl ether, steardimonium hydroxyethyl cellulose,raffinose, rhamsan, tapioca starch, whelan, levan, scleroglucan, sodiumalginate, stachylose, succinoglycan, wheat starch, xanthan gum, xylans,xyloglucans, and mixtures thereof. Microbial saccharides can be found inKirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol.16, John Wiley and Sons, NY pp. 578-611 (1994), which is incorporatedentirely by reference. Complex carbohydrates found in Kirk-OthmerEncyclopedia of Chemical Technology, Fourth Edition, Vol: 4, John Wileyand Sons, NY pp. 930-948, 1995 which is herein incorporated byreference.

The cosmetically acceptable composition of the present invention mayinclude surface-active agents. Surface-active agents includesurfactants, which typically provide detersive functionality to aformulation or act simply as wetting agents. Surface-active agents cangenerally be categorized as anionic surface-active agents, cationicsurface-active agents, nonionic surface-active agents, amphotericsurface-active agents and zwitterionic surface-active agents, anddispersion polymers. Anionic surface-active agents useful herein includethose disclosed in U.S. Pat. No. 5,573,709, incorporated herein byreference. Examples include alkyl and alkyl ether sulfates. Specificexamples of alkyl ether sulfates which may be used In this invention aresodium and ammonium salts of lauryl sulfate, lauryl ether sulfate,coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethyleneglycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highlypreferred alkyl ether sulfates are those comprising a mixture ofindividual compounds, said mixture having an average alkyl chain lengthof from about 12 to about 16 carbon atoms and an average degree ofethoxylation of from about 1 to about 6 moles of ethylene oxide. Anothersuitable class of anionic surface-active agents is the alkyl sulfuricacid salts. Important examples are the salts of an organic sulfuric acidreaction product of a hydrocarbon of the methane series, including iso-,neo-, and n-paraffins, having about 8 to about 24 carbon atoms,preferably about 12 to about 18 carbon atoms and a sulfonating agent,for example, sulfur trioxide or oleum, obtained according to knownsulfonation methods, including bleaching and hydrolysis. Preferred arealkali metals and ammonium sulfated C.sub.12-38 n-paraffins.

Additional synthetic anionic surface-active agents include the olefinsulfonates, the beta-alkyloxy alkane sulfonates, and the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide, as well as succinamates. Specific examples ofsuccinamates include disodium N-octadecyl sulfosuccinamate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;dioctyl esters of sodium sulfosuccinic acid.

Preferred anionic surface-active agents for use in the cosmeticallyacceptable composition of present invention include ammonium laurylsulfate, ammonium laureth sulfate, triethylamine lauryl sulfate,triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, and sodium dodecyl benzene sulfonate.

Amphoteric surface-active agents which may be used in the cosmeticallyacceptable composition of present invention include derivatives ofaliphatic secondary and tertiary amines, in which the aliphaticsubstituent contains from about 8 to 18 carbon atoms and an anionicwater solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate,or phosphonate. Representative examples include sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate as described in U.S. Pat.No. 2,658,072, N-higher alkyl aspartic acids as described in U.S. Pat.No. 2,438,091, and the products sold under the trade name MIRANOL. asdescribed in U.S. Pat. No. 2,528,378. Other sarcosinates and sarcosinatederivatives can be found in the CTFA Cosmetic Ingredient Handbook, FifthEdition, 1988, page 42 incorporated herein by reference.

Quaternary ammonium compounds can also be used in the cosmeticallyacceptable composition of the present invention as long as they arecompatible in the compositions of the invention, wherein the structureis provided in the CTFA Cosmetic Ingredient Handbook, Fifth Edition,1988, page 40. Cationic surface-active agents generally include, but arenot limited to fatty quaternary ammonium compounds containing from about8 to about 18 carbon atoms. The anion of the quaternary ammoniumcompound can be a common ion such as chloride, ethosulfate,methosulfate, acetate, bromide, lactate, nitrate, phosphate, or tosylateand mixtures thereof. The long chain alkyl groups can include additionalor replaced carbon or hydrogen atoms or ether linkages. Othersubstitutions on the quaternary nitrogen can be hydrogen, hydrogen,benzyl or short chain alkyl or hydroxyalkyl groups such as methyl,ethyl, hydroxymethyl or hydroxyethyl, hydroxypropyl or combinationsthereof.

Examples of quaternary ammonium compounds include but are not limitedto; Behentrimonium chloride, Cocotrimonium chloride, Cethethyldimoniumbromide, Dibehenyldimonium chloride, Dihydrogenated tallow benzylmoniumchloride, disoyadimonium chloride, Ditallowedimonium chloride,Hydroxycetyl hydroxyethyl dimonium chloride, HydroxyethylBehenamidopropyl dimonium chloride, Hydroxyethyl Cetyldimonium chloride,Hydroxyethyl tallowedimonium chloride, myristalkonium chloride, PEG-2Oleamonium chloride, PEG-5 Stearmonium chloride, PEG-15 cocoylquaternium 4, PEG-2 stearalkonium 4, lauryltrimonium chloride;Quaternium-16; Quaternium-18, lauralkonium chloride, olealkmoniumchloride, cetylpyridinium chloride, Polyquaternium-5, Polyquaternium-6,Polyquaternium-7, Polyquaternium-10, Polyquaternium-22,Polyquaternium-37, Polyquaternium-39, Polyquaternium-47, cetyl trimoniumchloride, dilauryidimonium chloride, cetalkonium chloride,dicetyldimonium chloride, soyatrimonium chloride, stearyl octyl dimoniummethosulfate, and mixtures thereof. Other quaternary ammonium compoundsare listed in the CTFA Cosmetic Ingredient Handbook, First Edition, onpages 41-42, incorporated herein by reference.

The cosmetically acceptable compositions of the present invention mayinclude long chain fatty amines from about C.sub.10 to C.sub.22 andtheir derivatives. Specific examples include dipalmitylamine,lauramidopropyldimethylamine, and stearamidopropyl dimethylamine. Thecosmetically acceptable compositions of this invention may also includefatty alcohols (typically monohydric alcohols), ethoxylated fattyalcohols, and di-tail phospholipids, which can be used to stabilizeemulsion or dispersion forms of the cosmetically acceptablecompositions. They also provide a cosmetically acceptable viscosity.Selection of the fatty alcohol is not critical, although those alcoholscharacterized as having fatty chains of C.sub.10 to C.sub.32, preferablyC.sub.14 to C.sub.22, which are substantially saturated alkanols willgenerally be employed. Examples include stearyl alcohol, cetyl alcohol,cetostearyl alcohol, myristyl alcohol, behenyl alcohol, arachidicalcohol, isostearyl alcohol, and isocetyl alcohol. Cetyl alcohol ispreferred and may be used alone or in combination with other fattyalcohols, preferably with stearyl alcohol. When used the fatty alcoholis preferably included in the formulations of this invention at aconcentration within the range from about 1 to about 8 weight percent,more preferably about 2 to about 6 weight percent. The fatty alcoholsmay also be ethoxylated. Specific examples include cetereth-20,steareth-20, steareth-21, and mixtures thereof. Phospholipids such asphosphatidylserine and phosphatidylcholine, and mixtures thereof mayalso be included. When used, the fatty alcohol component is included inthe formulations at a concentration of about 1 to about 10 weightpercent, more preferably about 2 to about 7 weight percent.

Nonionic surface-active agents, which can be used in the cosmeticallyacceptable composition of the present invention, include those broadlydefined as compounds produced by the condensation of alkylene oxidegroups (hydrophilic in nature) with an organic hydrophobic compound,which may be aliphatic or alkyl aromatic in nature. Examples ofpreferred classes of nonionic surface-active agents are: the long chainalkanolamides; the polyethylene oxide condensates of alkyl phenols; thecondensation product of aliphatic alcohols having from about 8 to about18 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide; the long chain tertiary amineoxides; the long chain tertiary phosphine oxides; the long chain dialkylsulfoxides containing one short chain alkyl or hydroxy alkyl radical offrom about 1 to about 3 carbon atoms; and the alkyl polysaccharide (APS)surfactants such as the alkyl polyglycosides; the polyethylene glycol(PEG) glyceryl fatty esters.

Zwitterionic surface-active agents such as betaines can also be usefulin the cosmetically acceptable composition of this invention. Examplesof betaines useful herein include the high alkyl betaines, such as cocodimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine,lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethylbetaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethylcarboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethylbetaine, stearyl bis-(2-hydroxypropyl)carboxymethyl betaine, oleyldimethyl gamma-carboxypropyl betaine, and laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines maybe represented by coco dimethyl sulfopropyl betaine, stearyl dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines andamidosulfobetaines, wherein the RCONH(CH.sub.2).sub.3 radical isattached to the nitrogen atom of the betaine are also useful in thisinvention.

The anionic, cationic, nonionic, amphoteric or zwitterionicsurface-active agents used in the cosmetically acceptable composition ofthe present invention are typically used in an amount from about 0.1 to50 percent by weight, preferably from about 0.5 to about 40 percent byweight, more preferably from about 1 to about 20 percent by weight.

The cosmetically acceptable compositions of the present invention mayinclude humectants, which act as hygroscopic agents, increasing theamount of water absorbed, held and retained. Suitable humectants for theformulations of this invention include but are not limited to: acetamideMEA, ammonium lactate, chitosan and its derivatives, colloidal oatmeal,galactoarabinan, glucose glutamate, glerecyth-7, glygeryth-12,glycereth-26, glyceryth-31, glycerin, lactamide MEA, lactamide DEA,lactic acid, methyl gluceth-10, methyl gluceth-20, panthenol, propyleneglycol, sorbitol, polyethylene glycol, 1,3-butanediol,1,2,6-hexanetriol, hydrogenated starch hydrolysate, inositol, mannitol,PEG-5 pentaerythritol ether, polyglyceryl sorbitol, xylitol, sucrose,sodium hyaluronate, sodium PCA, and combinations thereof. Glycerin is aparticularly preferred humectant. The humectant is present in thecomposition at concentrations of from about 0.5 to about 40 percent byweight, preferably from about 0.5 to about 20 percent by weight and morepreferably from about 0.5 to about 12 percent by weight.

The cosmetically acceptable compositions of the present invention mayinclude petrolatum or mineral oil components, which when selected willgenerally be USP or NF grade. The petrolatum may be white or yellow. Theviscosity or consistency grade of petrolatum is not narrowly critical.Petrolatum can be partially replaced with mixtures of hydrocarbonmaterials, which can be formulated to resemble petrolatum in appearanceand consistency. For example, mixtures of petrolatum or mineral oil withdifferent waxes and the like may be combined. Preferred waxes includebayberry wax, candelilla wax, ceresin, jojoba butter, lanolin wax,montan wax, ozokerite, polyglyceryl-3-beeswax,polyglyceryl-6-pentastearate, microcrystalline wax, paraffin wax,isoparaffin, vaseline solid paraffin, squalene, oligomer olefins,beeswax, synthetic candelilla wax, synthetic carnauba, synthetic beeswaxand the like may be blended together. Alkylmethyl siloxanes with varyingdegrees of substitution can be used to increase water retained by theskin. Siloxanes such as stearyl dimethicone, known as 2503 Wax, C30-45alkyl methicone, known as AMS-C30 wax, and stearoxytrimethylsilane (and)stearyl alcohol, known as 580 Wax, each available from Dow Corning,Midland, Mich., USA. Additional alkyl and phenyl silicones may beemployed to enhance moisturizing properties. Resins such as dimethicone(and) trimethylsiloxysilicate or Cyclomethicone (and)Trimethylsiloxysilicate fluid, may be utilized to enhance film formationof skin care products. When used, the petrolatum, wax or hydrocarbon oroil component is included in the formulations at a concentration ofabout 1 to about 20 weight percent, more preferably about 1 to about 12weight percent. When used, the silicone resins can be included fromabout 0.1 to about 10.0 weight percent.

Emollients are defined as agents that help maintain the soft, smooth,and pliable appearance of skin. Emollients function by their ability toremain on the skin surface or in the stratum corneum. The cosmeticallyacceptable composition of the present invention may include fatty esteremollients, which are listed in the International Cosmetic IngredientDictionary, Eighth Edition, 2000, p. 1768 to 1773. Specific examples ofsuitable fatty esters for use in the formulation of this inventioninclude isopropyl myristate, isopropyl palmitate, caprylic/caprictriglycerides, cetyl lactate, cetyl palmitate, hydrogenated castor oil,glyceryl esters, hydroxycetyl isostearate, hydroxy cetyl phosphate,isopropyl isostearate, isostearyl isostearate, diisopropyl sebacate,PPG-5-Ceteth-20, 2-ethylhexyl isononoate, 2-ethylhexyl stearate,C.sub.12 to C.sub.16 fatty alcohol lactate, isopropyl lanolate,2-ethyl-hexyl salicylate, and mixtures thereof. The presently preferredfatty esters are isopropyl myristate, isopropyl palmitate,PPG-5-Ceteth-20, and caprylic/capric triglycerides. When used the fattyester emollient is preferably included in the formulations of thisinvention at a concentration of about 1 to about 8 weight percent, morepreferably about 2 to about 5 weight percent.

The compositions of the present invention may also include siliconecompounds. Preferably, the viscosity of the silicone component is fromabout 0.5 to about 12,500 cps. Examples of suitable materials aredimethylpolysiloxane, diethylpolysiloxane,dimethylpolysiloxane-diphenylpolysiloxane, cyclomethicone,trimethylpolysiloxane, diphenylpolysiloxane, and mixtures thereof.Dimethicone, a dimethylpolysiloxane end-blocked with trimethyl units, isone preferred example. Dimethicone having a viscosity between 50 and1,000 cps is particularly preferred. When used, the silicone oils arepreferably included in the formulations of this invention at aconcentration of 0.1 to 5 weight percent, more preferably 1 to 2 weightpercent.

The cosmetically acceptable compositions of the present invention mayinclude volatile and non-volatile silicone oils or fluids. The siliconecompounds can be either linear or cyclic polydimethylsiloxanes with aviscosity from about 0.5 to about 100 centistokes. The most preferredlinear polydimethylsiloxane compounds have a range from about 0.5 toabout 50 centistokes. One example of a linear, low molecular weight,volatile polydimethylsiloxane is octamethyltrisiloxane. 200 fluid havinga viscosity of about 1 centistoke. When used, the silicone oils arepreferably included in the formulations of this invention at aconcentration of 0.1 to 30 weight percent, more preferably 1 to 20weight percent.

The cosmetically acceptable compositions of the present invention mayinclude volatile, cyclic, low molecular weight polydimethylsiloxanes(cyclomethicones). The preferred cyclic volatile siloxanes can bepolydimethyl cyclosiloxanes having an average repeat unit of 4 to 6, anda viscosity from about 2.0 to about 7.0 centistokes, and mixturesthereof. Preferred cyclomethicones are available from Dow Corning,Midland, Mich., and from General Electric, Waterford, N.Y., USA. Whenused, the silicone oils are preferably included in the formulations ofthis invention at a concentration of 0.1 to 30 weight percent, morepreferably 1 to 20 weight percent.

Silicone surfactants or emulsifiers with polyoxyethylene orpolyoxypropylene side chains may also be used in compositions of thepresent invention. Preferred examples include dimethicone copolyols and5225C Formulation Aids, available from Dow Corning, Midland, Mich., USAand Silicone SF-1528, available from General Electric, Waterford, N.Y.,USA. The side chains may also include alkyl groups such as lauryl orcetyl. Preferred are lauryl methicone copolyol. 5200 Formulation Aid,and cetyl dimethicone copolyol, known as Abil EM-90, available fromGoldschmidt Chemical Corporation, Hopewell, Va. Also preferred is lauryldimethicone, known as Belsil LDM 3107 VP, available from Wacker-Chemie,Munchen, Germany. When used, the silicone surfactants are preferablyincluded in the formulations of this invention at a concentration of 0.1to 30 weight percent, more preferably 1 to 15 weight percent. Aminefunctional silicones and emulsions may be utilized in the presentinvention. Preferred examples include Dow Corning 8220, Dow Corning 939,Dow Corning 949, Dow Corning 2-8194, all available from Dow Corning,Midland, Mich., USA. Also preferred is Silicone SM 253 available fromGeneral Electric, Waterford, N.Y., USA. When used, the amine functionalsilicones are preferably included in the formulations of this inventionat a concentration of 0.1 to 5 weight percent, more preferably 0.1 to2.0 weight percent.

[The cosmetically acceptable compositions of the present invention mayinclude volatile hydrocarbon oils. The volatile hydrocarbon comprisesfrom about C.sub.6 to C.sub.22 atoms. A preferred volatile hydrocarbonis an aliphatic hydrocarbon having a chain length from about C.sub.6 toC.sub.16 carbon atoms. An example of such compound includesisohexadecane, under the trade name Permethyl 101A, available fromPresperse, South Plainfield, N.J., USA. Another example of a preferredvolatile hydrocarbon is C.sub.12 to C.sub.14 isoparaffin, under thetrade name Isopar M, available from Exxon, Baytown, Tex., USA. Whenused, the volatile hydrocarbons are preferably included in theformulations of this invention at a concentration of 0.1 to 30 weightpercent, more preferably 1 to 20 weight percent.

The cosmetically acceptable compositions of the present invention mayinclude cationic and ampholytic conditioning polymers. Examples of suchinclude, but are not limited to those listed by the InternationalCosmetic Ingredient Dictionary published by the Cosmetic, Toiletry, andFragrance Association (CTFA), 1101 17 Street, N.W., Suite 300,Washington, D.C. 20036. General examples include quaternary derivativesof cellulose ethers, quaternary derivatives of guar, homopolymers andcopolymers of DADMAC, homopolymers and copolymers of MAPTAC andquaternary derivatives of starches. Specific examples, using the CTFAdesignation, include, but are not limited to Polyquaternium-10, Guarhydroxypropyltrimonium chloride, Starch hydroxypropyltrimonium chloride,Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7;Polyquaternium-14, Polyquaternium-15, Polyquaternium-22,Polyquaternium-24, Polyquaternium-28, Polyquaternium-32,Polyquaternium-33, Polyquaternium-36, Polyquaternium-37,Polyquaternium-39, Polyquaternium-45, Polyquaternium-47 andpolymethacrylamidopropyltrimonium chloride, and mixtures thereof. Whenused, the conditioning polymers are preferably included in thecosmetically acceptable composition of this invention at a concentrationof from 0.1 to 10 weight percent, preferably from 0.2 to 6 weightpercent and most preferably from 0.2 to 5 weight percent.

The cosmetically acceptable compositions of the present invention mayinclude one or more rheological modifiers. The rheological modifiersthat can be used in this invention include, but are not limited to highmolecular weight crosslinked homopolymers of acrylic acid, andAcrylates/C10-30 Alkyl Acrylate Crosspolymer, such as the Carbopol. andPemulen series, both available from B. F. Goodrich, Akron, Ohio, USA;anionic acrylate polymers such as Salcare and cationic acrylate polymerssuch as Salcare SC96, available from Ciba Specialties, High Point, N.C.,USA; Acrylamidopropylttrimonium chloride/acrylamide; Hydroxyethylmethacrylates polymers, Steareth-10 Allyl Ether/Acrylate Copolymer;Acrylates/Beheneth-25 Metacrylate Copolymer, known as Aculyn, availablefrom International Specialties, Wayne, N.J., USA; GlycerylPolymethacrylate, Acrylates/Steareth-20 Methacrylate Copolymer;bentonite; gums such as alginates, carageenans, gum acacia, gum arabic,gum ghatti, gum karaya, gum tragacanth, guar gum; guarhydroxypropyltrimonium chloride, xanthan gum or gellan gum; cellulosederivatives such as sodium carboxymethyl cellulose, hydroxyethylcellulose, hydroxymethyl carboxyethyl cellulose, hydroxymethylcarboxypropyl cellulose, ethyl cellulose, sulfated cellulose,hydroxypropyl cellulose, methyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose; agar; pectin; gelatin; starch andits derivatives; chitosan and its derivatives such as hydroxyethylchitosan; polyvinyl alcohol, PVM/MA copolymer, PVM/MA decadienecrosspolymer, poly(ethylene oxide) based thickeners, sodium carbomer,and mixtures thereof. When used, the rheology modifiers are preferablyincluded in the cosmetically acceptable composition of this invention ata concentration of from 0.01 to 12 weight percent, preferably from 0.05to 10 weight percent and most preferably from 0.1 to 6 weight percent.

The cosmetically acceptable composition of the present invention mayinclude one or more antioxidants, which include, but are not limited toascorbic acid, BHT, BHA, erythorbic acid, bisulfite, thioglycolate,tocopherol, sodium metabisulfite, vitamin E acetate, and ascorbylpalmitate. The anti oxidants will be present at from 0.01 to 5 weightpercent, preferably 0.1 to 3 weight percent and most preferably from 0.2to 2 weight percent of the cosmetically acceptable composition.

The cosmetically acceptable compositions of the present invention mayinclude one or more additional sunscreen active agents. Examples ofsunscreen active agents include, but are not limited to octylmethoxycinnamate (ethylhexyl p-methoxycinnamate), octyl salicylateoxybenzone (benzophenone-3), benzophenone-4, menthyl anthranilate,dioxybenzone, aminobenzoic acid, amyl dimethyl PABA, diethanolaminep-methoxy cinnamate, ethyl 4-bis (hydroxypropyl) aminobenzoate,2-ethylhexy 1-2-cyano-3,3-diphenylacrylate, homomethyl salicylate,glyceryl aminobenzoate, dihydroxyacetone, octyl dimethyl PABA,2-phenylbenzimidazole-5-sulfonic acid, triethanolamine salicylate, zincoxide, titanium oxide, zinc zeolite, titanium zeolite, and mixturesthereof. The amount of sunscreen used in the cosmetically acceptablecomposition of this invention will vary depending on the specific UVabsorption wavelength(s) of the specific sunscreen active(s) used, or tomeet certain governmental regulatory requirements of a specific countryor place.

The cosmetically acceptable compositions of the present invention mayinclude one or more preservatives. Example of preservatives, which maybe used include, but are not limited to 1,2-dibromo-2,4-dicyano butane(Methyldibromo Glutaronitrile, known as MERGUARD. Nalco ChemicalCompany, Naperville, Ill., USA), benzyl alcohol, imidazolidinyl urea,1,3-bis(hydroxymethyl)-5,5-dimethyl-2,3-imidazolidinedione (e.g., DMDMHydantoin, known as GLYDANT, Lonza, Fairlawn, N.J., USA.),methylchloroisothiazolinone and methylisothiazolinone (e.g., Kathon,Rohm & Haas Co., Philadelphia, Pa., USA), methyl paraben, propylparaben, phenoxyethanol, Chlorphenesin, usnic acid, natamycin, sodiumbenzoate, and mixtures thereof.

The cosmetically acceptable compositions of the present invention mayinclude any other ingredient by normally used in cosmetics. Examples ofsuch ingredients include, but are not limited to buffering agents,fragrance ingredients, chelating agents, color additives or dyestuffswhich can serve to color the composition itself or keratin, sequesteringagents, softeners, foam synergistic agents, foam stabilizers, sunfilters and peptizing agents.

The surface of pigments, such titanium dioxide, zinc oxide, talc,calcium carbonate or kaolin, can be treated with the unsaturatedquaternary ammonium compounds described herein and then used in thecosmetically acceptable composition of the present invention. Thetreated pigments are then more effective as sunscreen actives and foruse in color cosmetics such as make up and mascara.

The cosmetically acceptable compositions of the present invention can bepresented in various forms. Examples of such forms include, but are notlimited a solution, liquid, cream, emulsion, dispersion, gel, thickeninglotion.

The cosmetically acceptable compositions of the present invention maycontain water and also any cosmetically acceptable solvent. Examples ofacceptable solvents include, but are not limited to monoalcohols, suchas alkanols having 1 to 8 carbon atoms (like ethanol, isopropanol,benzyl alcohol and phenylethyl alcohol) polyalcohols, such as alkyleneglycols (like glycerine, ethylene glycol and propylene glycol) andglycol ethers, such as mono-, di- and tri-ethylene glycol monoalkylethers, for example ethylene glycol monomethyl ether and diethyleneglycol monomethyl ether, used singly or in a mixture. These solvents canbe present in proportions of up to as much as 70 percent by weight, forexample from 0.1 to 70 percent by weight, relative to the weight of thetotal composition.

The cosmetically acceptable compositions of the present invention canalso be packaged as an aerosol, in which case it can be applied eitherin the form of an aerosol spray or in the form of an aerosol foam. Asthe propellant gas for these aerosols, it is possible to use, inparticular, dimethyl ether, carbon dioxide, nitrogen, nitrous oxide, airand volatile hydrocarbons, such as butane, isobutane, and propane.

The cosmetically acceptable compositions of the present invention cancontain electrolytes, such as aluminum chlorohydrate, aluminum zirconiumchlorohydrate, alkali metal salts, e.g., sodium, potassium or lithiumsalts, these salts preferably being halides, such as the chloride orbromide, and the sulfate, or salts with organic acids, such as theacetates or lactates, and also alkaline earth metal salts, preferablythe carbonates, silicates, nitrates, acetates, gluconates, pantothenatesand lactates of calcium, magnesium and strontium.

Compositions of the present invention can include leave-on or rinse-offskin care products such as lotions, hand/body creams, shaving gels orshaving creams, body washes, sunscreens, liquid soaps, deodorants,antiperspirants, suntan lotions, after sun gels, bubble baths, hand ormechanical dishwashing compositions, and the like. In addition to thepolymer, skin care compositions may include components conventionallyused in skin care formulations. Such components include for example; (a)humectants, (b) petrolatum or mineral oil, (c) fatty alcohols, (d) fattyester emollients, (e) silicone oils or fluids, and (f) preservatives.These components must in general be safe for application to the humanskin and must be compatible with the other components of theformulation. Selection of these components is generally within the skillof the art. The skin care compositions may also contain otherconventional additives employed in cosmetic skin care formulations. Suchadditives include aesthetic enhancers, fragrance oils, dyes andmedicaments such as menthol and the like.

The skin care compositions of the present invention may be prepared asoil-in-water, water-in-oil emulsions, triple emulsions, or dispersions.

Preferred oil-in-water emulsions are prepared by first forming anaqueous mixture of the water-soluble components, e.g. unsaturatedquaternary ammonium compounds, humectants, water-soluble preservatives,followed by adding water-insoluble components. The water-insolublecomponents include the emulsifier, water-insoluble preservatives,petrolatum or mineral oil component, fatty alcohol component, fattyester emollient, and silicone oil component. The input of mixing energywill be high and will be maintained for a time sufficient to form awater-in-oil emulsion having a smooth appearance (indicating thepresence of relatively small micelles in the emulsion). Preferreddispersions are generally prepared by forming an aqueous mixture of thewater-soluble components, followed by addition of thickener withsuspension power for water-insoluble materials.

Compositions of the present invention for treating hair include bathpreparations such as bubble baths, soaps, and oils, shampoos,conditioners, hair bleaches, hair coloring preparations, temporary andpermanent hair colors, color conditioners, hair lighteners, coloring andnon-coloring hair rinses, hair tints, hair wave sets, permanent waves,curling, hair straighteners, hair grooming aids, hair tonics, hairdressings and oxidative products. The dispersion polymers may also beutilized in styling type leave-in products such as gels, mousses,spritzes, styling creams, styling waxes, pomades, balms, and the like,either alone or in combination with other polymers or structuring agentsin order to provide control and hair manageability with a clean,natural, non-sticky feel.

Hair care compositions of the present invention give slippery feel andthat can be easily rinsed from the hair due to the presence of thedispersion polymer, volatile silicones, other polymers, surfactants orother compounds that may alter the deposition of materials upon thehair.

In the case of cleansing formulations such as a shampoo for washing thehair, or a liquid hand soap, or shower gel for washing the skin, thecompositions of the present invention contain anionic, cationic,nonionic, zwitterionic or amphoteric surface-active agents typically inan amount from about 3 to about 50 percent by weight, preferably fromabout 3 to about 20-percent, and their pH is general in the range fromabout 3 to about 10.

Preferred shampoos of the present invention contain combinations ofanionic surfactants with zwitterionic surfactants and/or amphotericsurfactants. Especially preferred shampoos contain from about 0 to about16 percent active of alkyl sulfates, from 0 to about 50 weight percentof ethoxylated alkyl sulfates, and from 0 to about 50 weight percent ofoptional surface-active agents selected from the nonionic, amphoteric,and zwitterionic surface-active agents, with at least 5 weight percentof either alkyl sulfate, ethoxylated alkyl sulfate, or a mixturethereof, and a total surfactant level of from about 10 weight to about25 percent.

The shampoo for washing hair also can contain other conditioningadditives such as silicones and conditioning polymers typically used inshampoos. U.S. Pat. No. 5,573,709 provides a list of non-volatilesilicone conditioning agents that can be used in shampoos. Theconditioning polymers for use with the present invention are listed inthe Cosmetic, Toiletries and Fragrance Associations (CTFA) dictionary.Specific examples include the Polyquaterniums (example Polyquaternium-1to Polyquaternium-50), Guar Hydroxypropyl Trimonium Chloride, StarchHydroxypropyl Trimonium Chloride and Polymethacrylamidopropyl TrimoniumChloride.

Other preferred embodiments consist of use in the form of a rinsinglotion to be applied mainly before or after shampooing. These lotionstypically are aqueous or aqueous-alcoholic solutions, emulsions,thickened lotions or gels. If the compositions are presented in the formof an emulsion, they can be nonionic, anionic or cationic. The nonionicemulsions consist mainly of a mixture of oil and/or a fatty alcohol witha polyoxyethyleneated alcohol, such as polyoxyethyleneated stearyl orcetyl/stearyl alcohol, and cationic surface-active agents can be addedto these compositions. The anionic emulsions are formed essentially fromsoap.

If the compositions of the present invention are presented in the formof a thickened lotion or a gel, they contain thickeners in the presenceor absence of a solvent. The thickeners which can be used are especiallyresins, Carbopol-type acrylic acid thickeners available from B.F.Goodrich; xanthan gums; sodium alginates; gum arabic; cellulosederivatives and poly-(ethylene oxide) based thickeners, and it is alsopossible to achieve thickening by means of a mixture of polyethyleneglycol stearate or distearate or by means of a mixture of a phosphoricacid ester and an amide. The concentration of thickener is generally0.05 to 15 percent by weight. If the compositions are presented in theform of a styling lotion, shaping lotion, or setting lotion, theygenerally comprise, in aqueous, alcoholic or aqueous-alcoholic solution,the ampholyte polymers defined above.

In the case of hair fixatives, the composition of the present inventionmay also contain one or more additional hair fixative polymers. Whenpresent, the additional hair fixative polymers are present in a totalamount of from about 0.25 to about 10 percent by weight. The additionalhair fixative resin can be selected from the following group as long asit is compatible with a given dispersion polymer: acrylamide copolymer,acrylamide/sodium acrylate copolymer, acrylate/ammonium methacrylatecopolymer, an acrylate copolymer, an acrylic/acrylate copolymer, ad ipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymer, adipicacid/epoxypropyl diethylenetriamine copolymer, allyl stearate/VAcopolymer, aminoethylacrylate phosphate/acrylate copolymer, an ammoniumacrylate copolymer, an ammonium vinyl acetate/acrylate copolymer, an AMPacrylate/diacetoneacrylamide copolymer, an AMPDacrylate/diacetoneacrylamide copolymer, butyl ester of ethylene/maleicanhydride copolymer, butyl ester of PVM/MA copolymer, calcium/sodiumPVM/MA copolymer, corn starch/acrylamide/sodium acrylate copolymer,diethylene glycolamine/epichlorohydrin/piperazine-copolymer,dodecanedioic acid/cetearyl alcohol/glycol copolymer, ethyl ester ofPVM/MA copolymer, isopropyl ester of PVM/MA copolymer, karaya gum, amethacryloyl ethyl betaine/methacrylate copolymer, anoctylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, anoctylacrylamide/acrylate copolymer, phthalic anhydride/glycerin/glycidyldecanoate copolymer, a phthalic/trimellitic/glycol copolymer,polyacrylamide, polyacrylamidomethylpropane sulfonic acid, polybutyleneterephthalate, polyethylacrylate, polyethylene, polyquaternium-1,polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6,polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10,polyquaternium-11, polyquaternium-12, polyquaternium-13,polyquaternium-14, polyquaternium-15, polyquaternium-39,polyquaternium-47, polyvinyl acetate, polyvinyl butyral, polyvinylimidazolinium acetate, polyvinyl methyl ether, PVM/MA copolymer, PVP,PVP/dimethylaminoethylmethacrylate copolymer, PVP/eicosene copolymer,PVP/ethyl methacrylate/methacrylic acid copolymer, PVP/hexadecenecopolymer, PVP/VA copolymer, PVP/vinyl acetate/itaconic acid copolymer,shellac, sodium acrylates copolymer, sodium acrylates/Acrylnitrogenscopolymer, sodium acrylate/vinyl alcohol copolymer, sodium carrageenan,starch diethylaminoethyl ether, stearylvinyl ether/maleic anhydridecopolymer, sucrose benzoate/sucrose acetate isobutyrate/butyl benzylphthalate copolymer, sucrose benzoate/sucrose acetate isobutyrate/butylbenzyl phthalate/methyl methacrylate copolymer, sucrose benzoate/sucroseacetate isobutyrate copolymer, a vinyl acetate/crotonate copolymer,vinyl acetate/crotonic acid copolymer, vinyl acetate/crotonicacid/methacryloxybenzophenone-1 copolymer, vinyl acetate/crotonicacid/vinyl neodecanoate copolymer, and mixtures thereof. Syntheticpolymers used for creating styling aids are described in “The History ofPolymers in Haircare,” Cosmetics and Toiletries, 103 (1988),incorporated herein by reference. Other synthetic polymers that may beused with the present invention can be referenced in the CTFADictionary, Fifth Edition, 2000, incorporated herein by reference.

The cosmetically acceptable carrier contained in the cosmeticcompositions of the present invention may be varied depending on thetype of the formulation. For example, the formulation of ointment,pastes, creams or gels may comprise animal and vegetable fats, waxes,paraffins, starch, tragacanth, cellulose derivatives, polyethyleneglycols, silicones, bentonites, silica, talc, zinc oxide or mixtures ofthese ingredients.

In the formulation of powder or spray, it may comprise lactose, talc,silica, aluminum hydroxide, calcium silicate, polyamide powder andmixtures of these ingredients. Spray may additionally comprise thecustomary propellants, for example, chlorofluorohydrocarbons, propane,butane, diethyl ether, or dimethyl ether.

The formulation of solution and emulsion of the present invention maycomprise solvent, solubilizer and emulsifier, for example water,ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol,benzyl benzoate, propylene glycol, 1,3-butyleneglycol, oils, inparticular cottonseed oil, groundnut oil, maize germ oil, olive oil,castor oil and sesame seed oil, glycerol fatty esters, polyethyleneglycol and fatty acid esters of sorbitan or mixtures of theseingredients.

The formulation of suspension of the present invention may compriseliquid diluents, for example water, ethanol or propylene glycol,suspending agents, for example ethoxylated isosteary alcohols,polyoxyethylene sorbitol esters and poly oxyethylene sorbitan esters,micocrystalline cellulose, aluminum metahydroxide, bentonite, agar andtragacanth or mixtures of these ingredients.

The formulation of cleansing compositions of the present invention withsurfactant may comprise aliphatic alcohol sulfate, aliphatic alcoholether sulfate, sulfosucinnate monoester, isothionate, imidazoliumderivatives, methyltaurate, sarcocinate, fatty acid amide ether sulfate,alkyl amido betain, aliphatic alcohol, fatty acid glyceride, fatty aciddiethanolamide, vegetable oil, lanoline derivatives, ethoxylatedglycerol fatty acid ester or mixtures of these ingredients.

Additional antioxidant ingredients and compositions can be selectedfrom, but not limited to, Ascorbic acid, Ascorbic acid derivatives,Glucosamine ascorbate, Arginine ascorbate, Lysine ascorbate, Glutathioneascorbate, Nicotinamide ascorbate, Niacin ascorbate, Allantoinascorbate, Creatine ascorbate, Creatinine ascorbate, Chondroitinascorbate, Chitosan ascorbate, DNA Ascorbate, Carnosine ascorbate,Vitamin E, various Vitamin E derivatives, Tocotrienol, Rutin, Quercetin,Hesperedin (Citrus sinensis), Diosmin (Citrus sinensis), Mangiferin(Mangifera indica), Mangostin (Garcinia mangostana), Cyanidin (Vacciniummyrtillus), Astaxanthin (Haematococcus algae), Lutein (Tagetes patula),Lycopene (Lycopersicum esculentum), Resveratrol (Polygonum cuspidatum),Tetrahydrocurcumin (Curcuma longa), Rosmarinic acid (Rosmarinusofficinalis), Hypericin (Hypericum perforatum), Ellagic acid (Punicagranatum), Chlorogenic acid (Vaccinium vulgaris), Oleuropein (Oleaeuropaea), a-Lipoic acid, Niacinamide lipoate, Glutathione,Andrographolide (Andrographis paniculata), Carnosine, Niacinamide,Potentilla erecta extract, Polyphenols, Grapeseed extract, Pycnogenol(Pine Bark extract), Pyridoxine, Magnolol, Honokiol, Paeonol,Resacetophenone, Quinacetophenone, arbutin, kojic acid, and combinationsthereof.

The blood micro-circulation improvement ingredients and compositions canbe added to compositions of the present invention. These are selectedfrom Horse Chestnut Extract (Aesculus hippocastanum extract)), Esculin,Escin, Yohimbine, Capsicum Oleoresin, Capsaicin, Niacin, Niacin Esters,Methyl Nicotinate, Benzyl Nicotinate, Ruscogenins (Butchers Broomextract; Ruscus aculeatus extract), Diosgenin (Trigonella foenumgraecum,Fenugreek), Emblica extract (Phyllanthus emblica extract), Asiaticoside(Centella asiatica extract), Boswellia Extract (Boswellia serrata),Ginger Root Extract (Zingiber Officianalis), Piperine, Vitamin K,Melilot (Melilotus officinalis extract), Glycyrrhetinic acid, Ursolicacid, Sericoside (Terminalia sericea extract), Darutoside (Siegesbeckiaorientalis extract), Amni visnaga extract, extract of Red Vine (VitisVinifera) leaves, apigenin, phytosan, luteolin, and combinationsthereof.

The anti-inflammatory ingredients can be added to compositions of thepresent invention. These can be selected from at least one antioxidantclass of Cyclo-oxygenase (for example, COX-1 or COX-2) or Lipoxygenase(for example, LOX-5) enzyme inhibitors such as Ascorbic acid, Ascorbicacid derivatives, Vitamin E, Vitamin E derivatives, Tocotrienol, Rutin,Quercetin, Hesperedin (Citrus sinensis), Diosmin (Citrus sinensis),Mangiferin (Mangifera indica), Mangostin (Garcinia mangostana), Cyanidin(Vaccinium myrtillus), Astaxanthin (Haematococcus algae), Lutein(Tagetes patula), Lycopene (Lycopersicum esculentum), Resveratrol(Polygonum cuspidatum), Tetrahydrocurcumin (Curcuma longa), Rosmarinicacid (Rosmarinus officinalis), Hypericin (Hypericum perforatum), Ellagicacid (Punica granatum), Chlorogenic acid (Vaccinium vulgaris),Oleuropein (Olea europaea), alpha-Lipoic acid, Glutathione,Andrographolide, Grapeseed extract, Green Tea Extract, Polyphenols,Pycnogenol (Pine Bark extract), White Tea extract, Black Tea extract,(Andrographis paniculata), Carnosine, Niacinamide, and Emblica extract.Anti-inflammatory composition can additionally be selected from, but notlimited to, Horse Chestnut Extract (Aesculus hippocastanum extract)),Esculin, Escin, Yohimbine, Capsicum Oleoresin, Capsaicin, Niacin, NiacinEsters, Methyl Nicotinate, Benzyl Nicotinate, Ruscogenins (ButchersBroom extract; Ruscus aculeatus extract), Diosgenin (Trigonellafoenumgraecum, Fenugreek), Emblica extract (Phyllanthus emblicaextract), Asiaticoside (Centella asiatica extract), Boswellia Extract(Boswellia serrata), Sericoside, Visnadine, Thiocolchicoside, GrapeseedExtract, Ginger Root Extract (Zingiber Officianalis), Piperine, VitaminK, Melilot (Melilotus officinalis extract), Glycyrrhetinic acid, Ursolicacid, Sericoside (Terminalia sericea extract), Darutoside (Siegesbeckiaorientalis extract), Amni visnaga extract, extract of Red Vine(Vitis-Vinifera) leaves, apigenin, phytosan, luteolin, and combinationsthereof.

Certain divalent metal ions can be added to compositions of the presentinvention. The examples of such metal ions include zinc, copper,vanadium, chromium, cobalt, selenium, molybdenum, and iron.

EXAMPLES

The following examples are presented to illustrate presently preferredpractice thereof. These examples also include the formulation ofconsumer desirable lotion, cream, and other such compositions for theirretail marketing. As illustrations they are not intended to limit thescope of the invention. All quantities are in weight percent.

Example 1 In-Situ Preparation of Manganese (II) Urocanate

Ingredients. (1) Deionized water 96.49 (2) Manganese (II) Acetate 1.73(3) Urocanic acid 1.38 (4) Sodium Hydroxide 0.4. Procedure. Make mainbatch by mixing (1), (3), and (4) at 50 to 60 C. Add (2) and mix. Coolto room temperature. The mixture contains 1.9 percent by weight ofManganese urocanate.

Example 2 In-Situ Preparation of Manganese (III) Urocanate Acetate

Ingredients. (1) Deionized water 95.54 (2) Manganese (III) AcetateDihydrate 2.68 (3) Urocanic acid 1.38 (4) Sodium Hydroxide 0.4.Procedure. Make main batch by mixing (1), (3), and (4) at 50 to 60 C.Add (2) and mix. Cool to room temperature. The mixture contains 2.5percent by weight of Manganese (III) urocanate acetate.

Example 3 In-Situ Preparation of Manganese (II) Urocanate

Ingredients. (1) Deionized water 96.79 (2) Manganese (II) ChlorideMonohydrate 1.43 (3) Urocanic acid 1.38 (4) Sodium Hydroxide 0.4.Procedure. Make main batch by mixing (1), (3), and (4) at 50 to 60 C.Add (2) and mix. Cool to room temperature. The mixture contains 1.9percent by weight of Manganese urocanate.

Example 4 In-Situ Preparation of Manganese (II) Urocanate

Ingredients. (1) Deionized water 96.52 (2) Manganese (II) Sulfate 1.7(3) Urocanic acid 1.38 (4) Sodium Hydroxide 0.4. Procedure. Make mainbatch by mixing (1), (3), and (4) at 50 to 60 C. Add (2) and mix. Coolto room temperature. The mixture contains 2.5 percent by weight ofManganese (II) urocanate.

Example 5 In-Situ Preparation of Manganese (II) Urocanate Glycinate

Ingredients. (1) Deionized water 95.58 (2) Manganese bis-Glycinate 2.04(3) Urocanic acid 1.38. Procedure. Mix (1) to (3) at 50 to 60 C. Cool toroom temperature. The mixture contains 1 mMol of Manganese (II)urocanate glycinate.

Example 6 In-Situ Preparation of Manganese (II) Adenosine TriphosphateGlycinate

Ingredients. (1) Deionized water 95.58 (2) Manganese bis-Glycinate 2.04(3) Adenosine Triphosphate, Disodium hydrate 5.51 (anhydrous basis).Procedure. Mix (1) to (3) at 50 to 60 C. Cool to room temperature. Themixture contains 1 mMol of Manganese (II) adenosine triphosphateglycinate.

Example 7 In-Situ Preparation of Manganese (III) UrocanateMethanesulfonate

Ingredients. (1) Deionized water 94.34 (2) Manganese (III)

Methanesulfonate 3.88 (3) Urocanic acid 1.38 (4) Sodium Hydroxide 0.4.Procedure. Make main batch by mixing (1), (3), and (4) at 50 to 60 C.Add (2) and mix. Cool to room temperature. The mixture contains 1 mMolof Manganese (III) urocanate methanesulfonate.

Example 8 Peroxide Decomposing Sunscreen Cream

Ingredients. (1) Water 56.9 (2) Dicetyl Phosphate (and) Ceteth-10Phosphate 5.0 (3) Glyceryl Stearate (and) PEG-100 Stearate 4.0 (4)Phenoxyethanol 0.7 (5) Chlorphenesin 0.3 (60) Titanium Dioxide 0.2 (7)Sodium Hydroxide 0.5 (8) Magnolol 0.2 (9) Boswellia Serrata 0.5 (10)Benzophenone-3 4.0 (11) Manganese Urocanate 0.5 (12) Shea butter 2.0(13) Rosmarinic Acid 1.0 (14) Water 5.0 (15) Octyl methoxycinnamate 5.0(16) Polyamide-3 3.0 (17) 2,4-Dihydroxy Acetophenone (Resacetophenone)1.1 (18) Triethyl citrate 1.5 (19) EUK-134 0.1 (20) Cyclomethicone,Dimethicone Crosspolymer 2.0 (21) Zinc Zeolite 2.5 (22) Polysorbate-202.0 (23) Sepigel-305 2.0. Procedure. Mix (1) to (22) and heat at 70 to80 C till homogenous. Cool to 40 to 50 C. Cool to room temperature; add(23) to a desired viscosity. An off-white cream is obtained.

Example 9 Anti-Wrinkle Gel with Facial Peroxide Reduction

Ingredients. (1) Triethyl Citrate 67.00 (2) Ethylenediamine/HydrogenatedDimer Dilinoleate Copolymer Bis-D1-C14-18 Alkyl Amide 10.0 (3) XimeniaOil 0.1 (4) Sesamin 1.0 (5) Magnolol (and Honokiol 0.2 (6) Schisandrin0.5 (7) EUK-134 0.2 (8) Zinc Zeolite 20.0 (9) Fragrance 1.0. Procedure.Mix (1) and (2) and heat at 80 to 90 C till clear. Cool to 40 to 50 Cand add all other ingredients and mix. Cool to room temperature. Anoff-white gel-like product is obtained.

Example 10 Sunburn Prevention Gel

Ingredients. (1) C12-15 Alkyl Benzoate 92.00 (2) Dibutyl LauroylGlutamide 1.0 (3) EUK-134 0.1 (4) Triethyl citrate 5.0 (5) Magnolol (andHonokiol 0.2 (6) Manganese Urocanate Glycinate 0.5 (7)Tetrahydrocurcuminoids 0.2 (8) Silybin 1.0. Procedure. Mix (1) and (2)and heat at 95 to 110 C till clear. Cool to 40 to 50 C and add all otheringredients and mix. Cool to room temperature. A translucent gel-likeproduct is obtained.

Example 11 Skin Peroxide Reduction Anti-Wrinkle Sunscreen Lotion

Ingredients. (1) Water 69.36 (2) Acrylates/C10-30 Alkyl Acrylate

Crosspolymer 0.5 (3) EUK-134 0.1 (4) Sodium Stearyl Phthalamate 1.0 (5)Sodium Hydroxide 0.14 (6) Cetyl Alcohol 4.0 (7) Phenoxyethanol 0.7 (8)Chlorphenesin 0.3 (9) Octyl methoxycinnamate 5.0 (10) Ethylhexylglycein0.5 (11) Benzophenone-3 2.0 (12) PEG-6 10.0 (13) Tetrahydrocurcuminoids0.1 (14) Magnolol 0.1 (15) Paeonol 0.2 (16) Galanga Extract 5.0 (17)Fragrance 1.0. Procedure. Mix (1) to (11) and heat at 80 to 90 C tillclear. Cool to 45 to 55. Pre-mix (12) to (16) and add to main batch andmix. Cool to room temperature and adjust pH to 7.5.

Example 12 Sunburn Treatment Lotion

Ingredients. (1) Water 67.86 (2) Acrylates/C10-30 Alkyl AcrylateCrosspolymer 0.5 (3) Carnosine 0.1 (4) Sodium Stearyl Phthalamate 1.0(5) Sodium Hydroxide 0.14 (6) Cetyl Alcohol 4.0 (7) Phenoxyethanol 0.7(8) Sesamin 0.3 (9) Octyl methoxycinnamate 10.0 (10) Silybin 1.0 (11)Ethylhexylglycerin 0.5 (12) Polysorbate-20 2.0 (13) PEG-6 10.0 (14)Tetrahydrocurcuminoids 0.1 (15) EUK-134 0.1 (16) Manganese AdenosineTriphosphate 0.2 (17) Paeonol 0.5 (18) Fragrance 1.0. Procedure. Mix (1)to (17) and heat at 80 to 90 C till clear. Cool to 35 to 45. Add (18)and mix. Cool to room temperature and adjust pH to 7.5. A lotion isobtained.

Example 13 Sun-Block Gel with Heterocyclic Base Complex of Manganese

Ingredients. (1) Deionized water 20.0 (2) Zinc Zeolite 5.0 (3)Methylpropanediol 67.5 (4) Dimethicone copolyol 4.0 (5) Preservatives0.5 (6) Manganese Urocanate 1.0 (7) Ammonium Acryloyldimethyltaurate/VPcopolymer 2.0. Procedure. Make main batch by mixing (2) to (6) at roomtemperature. Pre-mix (1) and (7) to a clear paste and add to main batchwith mixing. The product has an off-white gel-like appearance.

Example 14 Sunscreen Fluid Composition

Ingredients. (1) PEG-6 85.4 (2) Vitamin A Palmitate 0.1 (3) Vitamin EAcetate 0.1 (4) Phenoxyethanol 0.5 (5) Propyl Paraben 0.3 (6) Sheabutter 1.0 (7) Apricot Kernel Oil 0.5 (8) Grapeseed Oil 0.5 (9) KiwiFruit Seed Oil 0.5 (10) Mango butter 0.5 (11) Hydroxypropyl Cellulose0.5 (12) Zinc Zeolite 10.0 (13) Manganese Urocanate Glycinate 0.5 (14)Darutoside 0.5 (15) Vitamin K 0.1. Procedure. Mix all ingredients to apaste.

Example 15 UV Absorbing Peroxide Decomposing Butter Composition

Ingredients. (1) Grapeseed Oil 15.8 (2) Mango Butter 18.5 (3) CocoaButter 0.5 (4) Beeswax 1.0 (5) Aloe butter 0.2 (6) Avocado Butter 0.5(7) Shea Butter 0.5 (8) Vitamin E 0.1 (9) Grapeseed Oil 2.0 (10)Dimethicone 1.0 (11) Hydrogenated Soybean Oil 35.0 (12) Sesame Oil 0.9(13) Tinoguard TT 0.2 (14) Phenoxyethanol 0.5 (15) Propyl Paraben 0.2(16) Zinc Zeolite 15.0 (17) Titanium Zeolite 2.0 (18) Esculoside 0.5(19) Manganese Urocanate Acetate 0.5 (20) Vitamin K 0.1 (21) Corn starch5.0. Procedure: Mix all ingredients and heat at 60 to 70 C. Cool to roomtemperature. A butter-like material is obtained.

Example 16 Sunscreen Emollient Paste

Ingredients. (1) Paraffin Wax 25.0 (2) Propyl Paraben 0.1 (3) CetylAlcohol 1.0 (4) GMS-SE 4.0 (5) Stearic Acid 3.0 (6) Polawax 5.0 (7)Deionized Water 44.0 (8) Methyl Paraben 0.2 (9) Aloe vera 0.2 (10)Triethanolamine 0.5 (11) Dimethicone/Dimethiconol 2.0 (12) Zinc Zeolite10.0 (13) Titanium Zeolite 4.0 (14) Manganese Urocanate 0.5 (15) EUK-1340.5. Procedure. Mix ingredients (1) to (11) and heat at 80 to 90 C to auniform mixture. Cool to 40 to 50 C. Add all other ingredients and mix.Cool to room temperature. An off-white paste is obtained.

Example 17 Sunscreen Powder

Ingredients. (1) Corn Starch 70.0 (2) Zinc Zeolite 14.0 (3) PEG-6 5.0(4) Titanium Zeolite 5.0 (5) Tetrahydrocurcumin 0.5 (6) ManganeseUrocanate Glycinate 0.5 (7) Dimethicone 5.0. Procedure. Mix (1) and (2).Premix (3) to (6) and add to main batch and mix. A powder composition isobtained.

Example 18 The Three-Step Topical Treatment Method

The three-step topical treatment method of the present inventioncomprises; (i) the mixing of a heterocyclic complex of manganese,wherein manganese is covalently bound to at least two oxygen atoms andcoordinately bound to at least two nitrogen atoms and having generalchemical structure according to FIG. 1, and (ii) a sunscreen agent, and(iii) topical application of said mixture, and wherein (iv) saidtreatment method is for the reduction of topical peroxide includinghydrogen peroxide. To illustrate this in practical terms, a compositionis prepared according to Example 1. It is mixed with a sunscreen agentin a desirable quantity. The mixture is applied to an area of skin wheredecomposition of topical peroxide is desired.

Example 19 The Three-Step Topical Treatment Method Using a SunscreenCream Base

The three-step topical treatment method of the present inventioncomprises; (i) the mixing of a heterocyclic complex of manganese,wherein manganese is covalently bound to at least two oxygen atoms andcoordinately bound to at least two nitrogen atoms and having generalchemical structure according to FIG. 1, and (ii) a sunscreen agent, and(iii) a carrier base, and (iv) topical application of said mixture, andwherein (v) said treatment method is for the reduction of sunburn andhydrogen peroxide. To illustrate this in practical terms, a compositionis prepared according to Example 8. The mixture is applied to an area ofskin where decomposition of topical peroxide is desired.

1. A heterocyclic complex comprising manganese, wherein said manganeseis covalently bound to at least two oxygen atoms and, wherein, said basehaving at least one nitrogen atom in its ring structure coordinatelybound to said manganese; wherein said complex is selected from the groupconsisting of manganese cis-urocanate, (I);

manganese cis-urocanate gluconate, (II);

manganese cis-urocanate glycinate, (III),

and combinations thereof.
 2. A composition comprising at least onecomplex of claim
 1. 3. A composition comprising at least one complex ofclaim 1 for the treatment of a skin condition selected from the groupconsisting of topical inflammation, damage from topical peroxide, anddamage from UVA, UVB, and UVC radiation.
 4. A composition comprising atleast one complex of claim 1 and a sunscreen agent.
 5. A compositioncomprising at least one complex of claim 1 further comprising a secondheterocyclic complex selected from the group consisting of manganeseadenosine triphosphate, manganese adenosine diphosphate, manganeseadenosine mono-phosphate, manganese adenosine triphosphate glycinate,manganese adenosine triphosphate amino acetate, manganese adenosinediphosphate amino acetate, manganese adenosine mono-phosphate aminoacetate, manganese benfotiamine glycinate, manganese benfotiamine,manganese benfotiamine amino acetate, manganese benfotiamine gluconate,((N,N′-bis(3-methoxysalcylidene)ethylenediamine))Manganese Chloride:EUK-134, and combinations thereof.
 6. The complex of claim 1, whereinsaid heterocyclic complex is manganese cis-urocanate of formula (I);


7. A composition comprising at least one complex of claim 1 furthercomprising a sunscreen agent selected from the group consisting of zincoxide, galanga extract, titanium dioxide, para-aminobenzoic acid,avobenzone, 3-benzylidene camphor, benzylidene camphor sulfonic acid,bisymydazilate, camphor benzalkonium methosulfate, polyquaternium-59,cinnamidipropyltrimonium chloride, diethylamino hydroxybenzoyl hexylbenzoate, diethylhexyl butamido triazone, dimethicodiethylbenzalmalonate, drometrizole trisiloxane, ecamsule, ensulizole, homosalate,isoamyl p-methoxycinnamate, 4-methylbenzylidene camphor, octocrylene,octyl dimethyl para-aminobenzoate, cinoxate, dioxybenzone, octylmethoxycinnamate, octyl salicylate, octyl triazone, oxybenzone, PEG-25para-aminobenzoate, polyacrylamidomethyl benzylidene camphor,sulisobenzone, methyl anthranilate, trolamine salicylate,benzophenone-3, benzophenone-4, bisoctrizole, bemotrizinol, zinczeolite, titanium zeolite, and combinations thereof.
 8. A compositionaccording to claim 7, wherein said sunscreen agent is benzophenone-3. 9.A composition comprising at least one complex of claim 1 furthercomprising a delivery system selected from the group consisting of awater and oil emulsion, a suspension, a colloid, a micro emulsion, asolution, a suspension of nanoparticles, an emulsion of nanoparticles,and an anhydrous composition.
 10. A method of treating a skin conditioncomprising the topical application of a composition comprising at leastone complex of claim 1 on an afflicted area, and wherein saidapplication is repeated as desired.
 11. The method of claim 10, whereinsaid skin condition is selected from the group consisting of damage fromperoxides; skin wrinkles; and damage from UVA, UVB, and UVC radiation.12. The composition of claim 5, wherein said second heterocyclic complexis manganese benfotiamine gluconate.
 13. The method of claim 11, whereinsaid skin condition is skin wrinkles.
 14. The complex of claim 1,wherein said heterocyclic complex is manganese cis-urocanate gluconateof formula (II);


15. The complex of claim 1, wherein said heterocyclic complex ismanganese cis-urocanate glycinate of formula (III);


16. A composition according to claim 5, wherein said second heterocycliccomplex is manganese adenosine triphosphate.
 17. The composition ofclaim 5, wherein said second heterocyclic complex is((N,N′-bis(3-methoxysalicylidene)ethylenediamine))Manganese ChlorideEUK-134.
 18. The composition of claim 3, wherein said treatment is fordamage from UVA, UVB, and UVC radiation.
 19. The composition of claim 9,wherein said delivery system is selected from the group consisting of awater and oil emulsion, a suspension, a colloid, a micro emulsion, asolution, a suspension of nanoparticles, an emulsion of nanoparticles,and an anhydrous composition.
 20. The composition of claim 19, whereinsaid delivery system is a water and oil emulsion.